Process of treating hydrocarbon oil with metallic halides



R. W. HANNA May 5, 1931.

PROCESS OF TREATING HYDROCABBON OIL WITH METALLIC HALIDES Filed Jan. 22. 1927 m u mij 2 33am u uznnwmm NUMEZUQZO Patented May 5, 1931 UNITED STATES PATENT OFFICE RICHARD W. HANNA, OF PIEDMONT, CALIFORNIA, ABSIGNOB TO STANDARD OIL COM- PANY OF CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION 01 DELA- WARE PROCESS OF TREATING HYDROCABBON OIL WITH IIETAIILIC KAI-IDES Application filed Ianuary 22, 1927. Serial No. 162,725.

This invention relates to a process of treating hydrocarbon oils with metallic halide and relates particularly to a process of converting hydrocarbon oils into lower boiling point oils by the catalytic action of such anhydrous metallic halides as aluminum ferric chloride, and the like.

In the treatment of hydrocarbon oils by metallic halides, there is formed as the result of the reaction a metallic halide residue, sludge, or coke which, if left in contact with unconverted h 'drocarbon oil at a reaction temperature for a substantial period of time, opprates to increase the percentage of coke w ich will be formed from the hydrocarbon oil and decrease the production of naphtha. Accordingly, it is the object of the present invention to provide a process for treating hydrocarbon oil with metallic halide in which the spent metallic halide or residual is maintained at a reaction temperature in contact with a hydrocarbon oil for only a comparatively short eriod of time.

In accordance with the process of the present invention, the hydrocarbon oil and metallic halide are first mixed together and then passed under a ressure suflicient to prevent vaporization 0 the unconverted oil, through a heating coil wherein they are heated to a reaction temperature, and thence passed into a reaction chamber and held under such pressure for a short period of time with or without mephanical agitation. Subsequently the admixture is passed to a chamber of larger diameter wherein the pressure is reduced and the gasoline produced separated with the simultaneous separation of the unconverted oil from the spent metallic halide. At the same time, any uns ent metallic halide is vaporized alon wit the unconverted oil and condense therewith. The unconverted oil and condensed metallic halide are then recirculated through the heating coil for continuous treatment. In this way, the required time for the metallic halide reaction is obtained without the unconverted hydrocarbon oil being maintained throughout its period of reaction in contact with the coke matter or spent metallic halide sludge. 'fiiereby it is found that the process results in both a higher yield of low boiling point oil and a lower yield of cokey matter or sludge.

The rocess of the present lnvention also prefera ly embodies the passage of the metallic halide and hydrocarbon oil admixture from the heating coil first into a reaction chamber before the passage of the material to the reduced ressure chamber and in said reaction chamber, a low level of the admixture is maintained at a reaction temperature with the simultaneous separation of produced naphtha. In this way, the major portion of the naphtha produced from the reaction is separated from the admixture and the admixture of unconverted oil and metallic halide is then passed to the reduced pressure chamber.

Various further objects and advantages of the present invention will be understood from a description of a preferred form or example of a process which embodies the invention. For this purpose, a process of the preferred type will be described as it is carried out with the apparatus illustrated in the accompanying drawing.

In the drawing:

The apparatus is diagrammatically indicated with the parts in elevation and mainly in vertical section.

In the apparatus, 2 indicates a mixer by which hydrocarbon oil and aluminumchloride or other metallic halide may be admixed, the mixer 2 being connected with a charger 3 for supplying metallic halide and with a line 4 having a pum 5 by which the hydrocarbon oil is supplie to the system. From the mixer 2, a line 6 having a pump 7 passes the admixture through a heating coil or zone 8. The heating coil 8 is indicated as mounted in a suitable heating means, such as a furnace 9 having a burner 10. From the coil 8, the admixture is passed into a. reaction chamber 11.

The reaction chamber 11 is preferably provided with agitating means 12 and may also be mounted over a furnace 13 having a burner 14 for supplying additional heat to the admixture if desired. The reaction chamber 11 is preferably provided with a vapor line 15 leading to a dephlegmator 16 and the dephlegmator 16 is provided with a reflux return line 17 to the reaction chamber 11. The dephle mator 16 is provided with a planer 18 by w ich water or other cooling medium may be used to control the temperature of the vapors discharged from the dephlegmator. The dephlegmator 16 is connected with a vapor line 19 leading through a condenser 20 to a tank or receiver 21 for holding gasoline or naphtha produced by the process. The tank 21 is provided with a valved vent line 22 by which the pressure upon the reaction chamber 11 dephlegmator 16. and condenser 20 may be controlled.

The reaction chamber 11 is provided with a liquid withdrawal line 23 which leads to a vaporizing chamber 24 which is also preferably mounted over a furnace 25 having a burner 26. The vaporizing chamber 24 is connected by a vapor line 27 with the dephlegmator 28. The dephlegmator 28 is in turn connected by a vapor line 29 with the condenser 30 and hence to a tank or receiver 31 for gasoline or naphtha separated from the oil at this point. The tank 31 is preferably connected with a line 32 includmg a vacuum pump 33 by which a reduced pressure less than atmospheric may be maintained on the vaporizing chamber 24, dephlegmator 28, and condenser 30. The line 23 preferably includes a pressure regulating or releasing valve 34. The line 32 preferably leads to the dephlegmator 16. The dephlcgmator 28 is also preferably connected by a line 35 to the source of feed oil to the system so that the feed oil to the system may be passed into the dephle mator 28 and be showered down against t e vapors rising therefrom and hence condense all the unconverted high boilin point oils and carry the same back to mixer 2. A by-pass line 36 is indicated by which the feed oil or part thereof may be bypassed around dephlegmator 28 in case the passage of all the feed oil to the dephlegmator 28 will not provide the correct temperature of discharge to vapors.

The preferred process as conducted with the apparatus thus described is-as follows: As the source of hydrocarbon oil to be employed, there may be employed any hydrocarbon oil whether petroleum, shale, or coal origin, but preferably I employ petroleum oil fractions of intermediate boihng point, for example, kerosene or gas oil fractions having a Beaum gravity of between 20 and 35. The process is preferably conducted continuously with the continuous passage of the hydrocarbon oil to the system and with the continuous addition of metallic halide, such as aluminum chloride, to the system through charger 3. The quantity of metallic halide added will depend upon various different conditions, such as the character of oil and the extent of conversion desired but preferably ranges between .2 to 1 pound of metallic halide per gallon of hydrocarbon oil to be treated.

Within the heating coil 8, the admixture is continuously heated to a reaction temperature, which is usually between 500 and 700 F., and most desirably between 550 and 600 F and preferably at a pressure substantially above atmospheric. Within the reaction chamber 11 only a portion of the ultimate conversion is permitted to take place before withdrawal of the oil from said chamber. Thus, where the ultimate reaction will result in the yield of 60 to 75 per cent. of naphtha from the oil charged to the system, only about 10 per cent. of the naphtha is withdrawn from reaction chamber 11 during the first passage of oil therethrough in order to avoid the maintenance of the unconverted oil in prolonged contact with the sludge produced from the conversion reaction. For this purpose, the level of the admixture maintained in the reaction chamber is maintained below center and preferably near the bottom of the reaction chamber so that on account of the small volume of admixture in the reaction chamber 11, it will be sufliciently rapidly removed therefrom through line 23 so as to prevent prolonged heating of any portion of the sludge formed.

The admixed material withdrawn from reaction chamber 11 is passed into still 24 where the pressure is reduced so that the major portion of the h drocarbon oil is readily vaporized from t e admixture and thus decreased in term erature. The still 24 is preferably provide with a stirrer 37 for agltating the contents therein. Additional heat may be supplied to drive out all of the remaining hydrocarbon oil from the metallic halide sludge and reduce the same to a coke. All of the unconverted oils vaporize from the still 24 and are condensed by the action of the feed oil, the heat of said vapors being imparted to the feed oil whereby the vapors may be recirculated through the apparatus without great loss in heat econom for another or further reaction with meta lic halide. If there is withdrawn through line 23 any portion of metallic halide which has not expended its strength, or not converted into a cokey or tarry mass, said metallic halide would be vaporized in still 24 and condensed with the feed oil and condensed vapors in dephlegmator or reflux tower 28 and recirculated back into reaction chamber 11. Any naphtha produced in still 24 is separated from the condensed oils and passed into the storage vessel 31 inasmuch as the still 24 and vapor separating apparatus connected therewith is operated sometimes under vacuum in order to prevent loss of vapors. The uncondensed vapors from re ceiver 31 are forced through line 32 into the condensed oils in reflux tower 16 wherein they are absorbed and condensed under the pressure of this portion of the system.

The pressures of operation throughout the system or process will vary according to the oil being treated and the character of the products desired. However, the following operating conditions ma be given as examples. The pressure on the reaction chamber 11, dephlegmator 16 and tank 21 is regulated by gas release valve on line 22. A suitable operating pressure when cracking A. P. 1. oil would be twenty pounds gauge on the release line 22. The pressure on the reaction chamber 11 would be slightly hi her, say 23 pounds due to the pressure rop through dephlegmator 16 and condenser 20. The pressure in coil 8 is the same as that in reaction chamber 11, except that it is slight- 1y higher due, to the pressure drop in the line between coil 8 and chamber 11. This pressure is sufiicient to substantially prevent vaporization of the unconverted oil. The vacuum in still 24 is controlled by the pump 33. The vacuum at the pump will usually be about two inches higher than that at the still 24 due to friction losses in pipes 30, 37 and dephlegmator 28. For example, with a suitable vacuum of twenty-six inches at the pump, the vacuum at the still 24 would be twenty-four inches.

It is found that by conducting the metallic halide reaction so that the particles of metallic halide sludge or coke are removed from the system rapidly after being formed, the efiiciency of the metallic halide 1s greatly increased and also the quantity of coke or tar formed decreased and the quantity of naphtha or motor fuel which can be produced from a given character of oil with a given quantity of metallic halide is substantiall increased.

ile the process of treating h drocarbon oil with metallic halide herein escribed is well adapted for carrying out the objects of the present invention, it is understood that various modifications and changes may be made without departing from the spirit of the invention and the invention includes all such modifications and changm as come, within the scope of the following appended claims.

I claim:

1. A process of treating hydrocarbon oil with metallic halide to convert relatively high boiling point oil to relatively low boiling point oil which com rises passing a mixture of hydrocarbon oi and metallic halide under a pressure suflicient to prevent the unconverted relatively high boiling point oil from vaporizing through a heating coil wherein said admixture is heated to a reaction temperature, passing the admixture into a reaction chamber where the admixtureismamtainedforaperiodoftimeat the reaction temperature, thereafter passing metallic halide residue from said reaction chamber together with some hydrocarbon oil into a chamber of larger diameter wherein the pressure is reduced and hydrocarbon oil vaporized from the inactive metallic halide residue, passing the vapors to a dephlegmating tower, therein condensing the unconverted higher boiling point oils, and returning said oils to the heating coil in absence of the portion of metallic halide residual which has become inactive.

2. A process of treating hydrocarbon oils with metallic halide to convert relativel high boiling point oil to relatively low boi ing point oil which comprises passing a mixture of hydrocarbon oil and metallic halide under a pressure sufficient to prevent the unconverted relatively hi h boiling point oil from vaporizing throug a heating coil wherein the same is heated to a reaction temperature, passing the admixture into a reaction chamber wherein the admixture is maintained for a period of time at the reaction temperature, removing produced low boilin point oils as vapors rom said reaction 0 amber then passing admixed hydrocarbon oil and metallic halide to a chamber maintained under a substantially reduced pressure, wherein the hydrocarbon oil is vaorized from the metallic halide residue rendered inactive condensing unconverted higher boilin points oils from the vapors vaporized rom said metallic halide and returning said oils to the reaction chamber.

3. A process of treating hydrocarbon oil with metallic halide to convert relatively high boiling point oil to relatively low boiling point 011 which comprises passing hydrocarbon oil and metallic halide under pressure sufiicient to maintain the relatively igh boiling point oil from vaporizing through a heating coil and hence into a reaction chamber wherein the admixture is maintained at the reaction temperature and such ressure and at a low level within the cham r, withdrawing vapors from said reaction chamber, withdrawing the admixed residual metallic halide and heavy oil from said reaction chamber, passing the residual metallic halide and relatively high boiling point oil into a chamber maintained substantially at reduced pressure, therein vaporizin the unconverted hydrocarbon oils from t e metallic halide rendered inactive and contacting said unconverted hydrocarbon oil vapors with the fresh oil supplied to the system, whereby the unconverted hydrocarbon oils are condensed and returned through the heating coil to the reaction chamber in the absence of metallic halide which has been rendered inactive.

4. A process of treating hydrocarbon oil with metallic halide to convert relatively high boiling point oil into relatively low boiling point oil which comprises heating the admixture of hydrocarbon oil and metallic halide to a reaction temperature, at a pressure sufficient to maintain the relatively high boiling point oil from vaporizing, passing said admixture to a reaction chamber in which a small volume of the admixture is maintained at such pressure and in which the produced low boiling point hydrocarbon oils are vaporized and from which admixed residual metallic halide and oil is continuously withdrawn, passing the vapors to a dephlegmator, passing the withdrawn mixture to a reduced pressure chamber, vaporizing all of the hydrocarbon oil of said admixture leaving as an unvaporized residue, the metallic halide which has been rendered inactive, passing said vapors to a dephlegmator, and therein introducing sufficient feed oil to the system to condense the unconverted high boiling point hydrocarbon vapors.

5. A process of treating hydrocarbon oil with metallic halide for converting relativel high boiling point oil into relatively low oiling point oil which comprises heating the admixture of hydrocarbon oil and metallic halide to a reaction temperature at a pressure suflicient to prevent the relatively high boiling point oil from vaporizing, passing said admixture to a reaction chamber in which a small volume of the, admixture is maintained at such pressure and in which the produced low boilin point hydrocarbon oils are vaporized and rom which admixed metallic halide and oil is continuously withdrawn, passing the vapors to a dephlegmator, passing the withdrawn mixture to a chamber, maintaining such chamber under a pressure below that maintained in the reaction chamber, vaporizing all of the hydrocarbon oil of said admixture, leaving as an unvaporized residue, the metallic halide which has been rendered inactive, passing said vapors to a dephlegmator, therein introducing sufficient feed oil to the system to condense the unconverted high boiling point hydrocarbon oils, and passing uncondensed vapors from the second dephlegmator into the first mentioned dephlegmator.

6. A process of treating hydrocarbon oils with metallic halide to convert relatively high boiling point oil into relatively low boiling point oil which comprises heating an admixture of hydrocarbon oil and metallic halide to a reaction temperature under a pressure above atmospheric suflicient to prevent the relatively high boiling point oil from vaporizing, passing the admixture at such pressure to a reaction chamber in which produced low boilin point hydrocarbons are vaporized from 51c admixture and in which a small volume of admixture is maintained, assing the residual metallic halide and oil roin said chamber and reducing the pressure thereon to a ressure below atmospheric, thereby vaporizing and se arating the unconverted hydrocarbon oils i i'om the spent metallic halide, and condensing and returning said oils through the heating zone to the reaction chamber.

7. A process of treating hydrocarbon oil with metallic halide to convert relatively high boiling point oil to relatively low boiling point oil which comprises heating hydrocarbon oil and metallic halide to a reaction temperature and under a pressure greater than atmospheric sufiicient to maintain the relatively high boiling point oil from vaporizin passing the admixture to a reaction cham er wherein it is maintained at the reaction temperature and at such pressure while the produced low boiling point oils are vaporized therefrom, passing admixed hydrocarbon oils and metallic halide from said reaction chamber to a chamber maintained under a ressure less than atmospheric, therein vaporizing the unconverted hydrocarbon oils from the metallic halide, and commingling said vapors with fresh oil introduced to the system whereby said vapors are condensed and returned to the reaction chamber.

8. A process of treating hydrocarbon oils with a metallic halide to convert relatively high boiling point oil to relatively low boiling point oil which comprises passing a mixture of hydrocarbon oil and metallic halide under pressure suflicient to prevent the rela tively high boiling point oil from vaporizing through a heating coil wherein the same is heated to a reaction temperature, passing the admixture into a reaction chamber wherein the admixture is maintained at such pressure for a period of time at the reaction temperature, which will permit only a small portion of the oil to react with the metallic halide in one passage through said chamber, vaporizing produced lower boiling point oil from the reaction chamber continuously, passing admixed hydrocarbon oil and metallic halide residue to a chamber maintained under a substantially reduced pressure, therein vaporizin the hydrocarbon oil and unspent metallic ialide from the spent inactive metallic halide residual, and condensing and recycling the hydrocarbon oil and unspent metallic halide through the heating coil to said reaction chamber.

9. A continuous process of treating hydrocarbon oils with metallic halide to convert relatively high boiling point oil into relativel low boiling point oil which comprises continuously heating an admixture of hydrocarbon oil and metallic halide and passing the same under pressure sufiicient to maintain the relatively high boiling point oil from vaporizing into a reaction chamber wherein the admixture is heated for a short period of time suflicient to effect only a partial reaction of the metallic halide on the hydrocarbon oil in one passage through the reaction chamber, vaporizing from said chamber produced low boiling oint oils continuously withdrawing admixe hydrocarbon oil, metallic halide and metallic h alide residue from said reaction chamber, continuously reducing the pressure upon said mixture and vaporizing the hydrocarbon oil and metallic halide from residual and s ent inactive metallic halide, and condensing and continuously passing said hydrocarbon oil through the heating zone and unspent metallic halide with the fresh oil to the reaction chamber.

10. A continuous process of treating hydrocarbon oils with metallic halide to convert relatively high boiling ,point oil into relatively low boilin point 011 which cornprises continuously ieating an admixture of hydrocarbon oil and metallic halide under pressure sufiicient to prevent the relatively high boiling point oil from vaporizing and passing the same under such pressure into a reaction chamber wherein the admixture is heated for a short period of time sufficient to effect only a partial reaction of the metallic halide on the hydrocarbon oil in one passage throu h the reaction chamber, continuously with rawing admixed hydrocarbon oil, metallic halide and metallic halide residue from said reaction chamber, continuously reducing the pressure upon said mixture and vaporizing the hydrocarbon oil and unspent metallic halide from residual and spent inactive metallic halide, and condensing and continuously passing such hydrocarbon oil and unspent metallic halide with the fresh oil through to the reaction chamber, the rate of fresh oil to the reaction chamber bein considerabl less than the rate of rec chn hydrocar on oil separated from t e a mixture withdrawn from the reaction chamber.

Signed at San Francisco this 7th day of January, 1927.

RICHARD W. HAN NA.

tial reaction of the metallic halide on the hydrocarbon oil in one passage through the reaction chamber, vaporizing from said chamber produced low boiling oint oils continuously withdrawing admixe h drocarbon oil, metallic halide and metallic alide residue from said reaction chamber, continuously reducing the pressure upon said mixture and vaporizing the h drocarbon oil and metallic halide from resi ual and spent inactive metallic halide, and condensing and continuously passing said hydrocarbon oil through the heating zone and unspent metallic halide with the fresh oil to the reaction chamber.

10. A continuous process of treating hydrocarbon oils with metallic halide to convert relatively high boiling point oil into relatively low boilin point 011 which comprises continuously ieating an admixture of hydrocarbon oil and metallic halide under pressure suflicient to prevent the relatively high boilin point oil from vaporizing and passing t e same under such pressure into a reaction chamber wherein the admixture is heated for a short period of time sufiicient to eifect only a partial reaction of the metallic halide on the hydrocarbon oil in one passage throu h the reaction chamber, contlnuously with rawing ad mixed hydrocarbon oil, metallic halide and metallic halide residue from said reaction chamber, continuously reducing the pressure upon said mixture and vaporizing the hydrocarbon oil and unspent metallic halide from residual and spent inactive metallic halide, and condensing and continuously passing such hydrocarbon oil and unspent metallic halide with the fresh oil through to the reaction chamber, the rate of fresh oil to the reaction chamber being considerably less than the rate of rec clm hydrocar on oil separated from the a mixture withdrawn from the reaction chamber.

Signed at San Francisco this 7th day of January, 1927.

' RICHARD W. HAN NA.

CERTIFICATE OF CORRECTION.

Patent No. l, 803, 670.

RICHARD W. HANNA.

Granted May 5, 1931, to

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 4, lines 42 to 44, claim 5, strike out the words and comma "leaving as an unvaporized residue, the metallic halide which has been rendered inactive,"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of October,, A. D. 1931.

CERTIFICATE OF CORRECTION.

Patent No. 1,803,670. Granted May 5, 1931, to

RICHARD W. HANNA.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 4, lines 42 to 44, claim 5, strike out the words and comma "leaving as an unvaporized residue, the metallic halide which has been rendered inactive, and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 6th day of October, A. D. l93l. 

